Process for breaking emulsions employing lactone-derived compounds of certain oxyalkylated resins



y 26, 1 M. DE GROOTE ETAL 2, 0

PROCESS F OR BREAKING EMULSIONS EMPLOYING LACTONE-DERIVED COMPOUNDS OF CERTAIN OXYALKYLATED RESINS Filed Oct. 5. 1953 PHENOL-ALDEHYDE 0 o v RESIN 100% INV United States Patent PROCESS FOR BREAKING EM-ULSIONS 'EMPLOY ING LACTONE-DERIVED COMPOUNDS OF 'CER- TAIN OXYALKYLATED RESINS' 8 Claims. Cl. 252-342 This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-in-oil type and particularly petroleum emulsions.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the Water-in-oil type, that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines'. Controlled emul'sification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly, inorganic salts,

from pipeline oil;

The present invention is concerned with a process for breaking petroleum emulsions employing a demulsifier 2,888,403 Patented May 26, 1959 2 the same purpose and particularly for the resolution of petroleum emulsions of the water-in-oil type.

As far as we are aware the only suitable beta-lactone commercially available is beta-propiolactone'. Other simi-' lar lactones and particularly those having'less than 6 carbon atoms, such as beta-butyrolactone and betamethyl-beta-butyrol'acton'e, can be prepared by any well known procedure such as described, for example, in1U2S; Patent No. 2,469,110, dated May 3, 1949, to Hagemeyer Jr.

A number of other beta-.lactones could be employed and particularly those having less than 6 carbon atoms. Stated another way, the lactones which are suitable are the beta-la'ctones of monocarboxylic acids having at least one unsubstituted hydrogen atom on the alpha-carbon atom and containing only unreactive hydrocarbon substituents. structurally, these beta-lactones' possess the formula Included inthis class oficompounds are the beta-lacton'es of saturated aliphatic monocarboxylic acidscontaining at least one hydrogen atom on the alpha. carbon atom such including products obtained by chemically modifying certain polyols, as hereinafter specified, with beta propiol'actone, or its equivalent, under substantially anhydrous conditions in the absence of a basic catalyst andpreferably in the presence of an acid catalyst, to yield fusible (non-thermosetting)' derivatives. The polyols employed are oxyalkylated hydrophilesynthetic derivatives of certain phenol-aldehyde resins.

The-preparation of hydrophile synthetic products, which are inessence polyols by the oxyalkylation of phenolaldehyde resins is well known and has been described in considerable detail in a large number of United States patents; for instance, United States Patents Nos. 2,499,365, 2,499,366, 2,499,367, 2,499,368 and 2,499,370, all dated March 7, 1950, and all to De Groote and Keiser. The preferred types of those particularly suitable for the present purpose are those described in the last mentioned patents with the proviso that the substituent radical may have as many as 18 carbon atoms. Reference is made also to U.S. Patent No. 2,557,081 dated June, 1951', to De Groote and Keiser.

Briefly stated, the manufacturing method herein employed is to react an oxyalkylated phenol resin of the kind described in the various above mentioned patents with beta-propiolactone or its equivalent in a ratio so there are employed preferably at least two moles 'of the lactone for each oxyalkylated resin molecule.

In our co-pending applications, Serial Nos. 343,804, filed March 20, 1953 (now abandoned), and 349,972, filed April 20, 1953 (now U.S. Patent 2,792,353, dated May 14, 1957), we have described more complicated oxyalkylation derivatives in which oxyalkylated resins were united by means of a polyepoxide, particularly a diglycidyl ether. Such polyepoxide derivatives also may 0 be treated with a suitable beta-lactone 1n the manner herein described. The resultant products are suitable for v r as beta-propiolactone, beta-butyrolactone, alpha-methylbcta-propiolactone, beta-valerolactone, alphax methyl-butyrolactone, alpha-ethyl-beta-propiolactone, beta-isovalerolactone, betarn-caprola-ctone, alpha-methyl-beta-valerolactone, beta-methyl-beta-ethyl-beta-propiolactone; alphamethyl-beta-ethyhbeta-propiolactbne, alpha-*1methyl-beta methyl-beta-propiolactone, alpha-propyl-betafpropiolac tone, alpha-butyl-beta-propiolactone, beta-methyl-betapropyl-beta-propiolactone and the like; the beta-lactones of aryl-substituted carboxylic acids such as beta-phenylbeta-propiolactone, alpha-phenyl-beta-propiolactone, and other beta-lactones of substituted carboxylic acids such as beta-cycl'ohexyl-beta-propiolactone,. beta-benzyl-betapropiolactone, alpha-cyclohexyl-beta-propiolactone and the. like. The preferred compounds are the beta-lactones containing less than 6' carbon atoms, particularly the low molecular weight aliphatic beta-lactones since the difliculty of carrying out the reaction is increased'when eniploying lactones of'higher molecular weight.

Reference is made to the fact that no attempthasbeen made to point out the. exact nature, at least quantitatively, of the modification which takes place when a polyol is reacted with beta-propiolactone. or the-like. The procedure simply has been referred to as chemically modifying the polyol.

Returning now to a comparable reaction, except'that .obviously it is more simple, is the one involving a mono- In all these reactions a certain amount. of polymeric material, e.g.

Cl.CH .CH .COO (CH .CI-I .COO) CHQCH COQ'I- CHr-O is formed.

(See Chemistry of Carbon Compounds, Rodd, I part B, Elsevier Publishing Co., New York,,.N. Y.,,,1952,

p. .Jj-J 3 Even when a reaction is conductedqundeng ideal conr ,the formula appear.

paring the resinous polymers of my invention.

-apolyhydric alcohol.

ditions using as simple reactant a methanol in large excess the yield of the beta-alkoxymonocarboxylic acid obtained may be 70% and often considerably less. See US. Patent No. 2,352,641, dated luly 4, 1944, to Kiing.

In the case of a monohydric reactant employing acid asa catalyst three types of reactions take place, dependingon whether the 4-membered ring splits between the oxygen atom andthe carbonyl carbon atoms, or the oxygen atom and the adjacent methylene carbon atom. This has been illustrated sometime, thus:

3 (SeeB. F.,Goodrich Chemical Company Service Bulletin 47-SD5, November 1, 1947.) Dehydration, of course, depends on the temperature employed and other conditions. See also Journal of Americal Chemical Society, Vol-70, page 1004 (1948).

. ,The third reaction is simply one of polymerization as has been pointed out in US. Patent No. 2,526,554, dated Octoberl'l, 1950, to Gresham and Jansen. For instance,

the patent states as follows:

. Polyester-acids produced by the reaction of an excess ofbeta-propiolactone with an alkanol (R -0H) in the presence of an acid catalyst. Such polyester acids possess .propyl, butyl, etc."

, When a more complicated reactant is employed, as in the present instance, i.e., a certain specified variety of a polyhydric alcohol is used, further complications may It is necessary to only point out that a free carboxyl radical. resulting from a reaction of the kind previously described, could combine with an unconverted alcoholic hydroxyl to form a polyester. Indeed, the best statement in regard to the situation involving propionolactone or itscquivalent and polyhydroxy compounds is stated in US. Patent No. 2,455,731, dated December 7, 1948, to' Caldwell, in the following language:

It is known that beta-lactones react with monohydric alcohols to produce beta -alkoxy carboxylic acids which 2m 6 free hydroxyl groups to produce valuable polymers which may be readily adapted to forming films, incorporated with cellulose esters, cellulose ethers, vinyl polymers, and the like. Other beta-laotones, similar in structure to beta-propionolactone, are not suitable for pre- It was thereforemost unexpected to find that beta-propionolactone alone gave valuable polymers when reacted with Although the mechanism of the condensation has not been fully investigated, it appears that beta-propionolactone undergoes some peculiar form of rearrangement or molecular orientation which is not shown by the higher members of the beta-lactone series.

Actually, the situation is more involved than suggested by what has been said previously, by reference to the above patents. See Journal American Chemical Society, volume 70, page 1004 (1948), and Journal American Chemical Society, volume 73, page 4273 (1951).

As far as we have been able to determine we have found no condition under which one could, for example, introduce a single carboxyl radical for each reactive hydroxyl radical present without simultaneously producing one or more other derivatives in an amount equivalent to the carboxy derivative. In other words, starting with a ratio of one mole of beta propiolactone, for example, for each reactive hydroxyl we have found that in all likelihood at least five cogeneric types may be formed: (1) a monocarboxylated derivative; (2) an ester formed by reaction between the monocarboxylated derivative and a hydroxyl group; (3) a hydroxy propionic acid ester; (4) an acid group of the type where 2 carboxyls have entered at a single hydroxyl position rather than one, thus ROCH CH COOCH CH COOH such reaction involving two moles of beta propiolactone at a single hydroxyl position means, of course, there is a residual carboxyl; however, this more complex type of carboxylic acid can in turn form an ester just the same as the simpler type; (5) and thus representing a fifth type present in the cogeneric mixture. Actually, the conventional titration between the methyl orange end point and the phenolphthalein end-point does not reveal the simple carboxylic acid alone but may reveal the type noted above where two beta lactone molecules enter at a single hydroxyl position. Likewise, when an increased ratio of beta-lactone is employed the type of acid depicted above may become more complicated. In other words, several moles of beta propiolactone may enter at a single hydroxyl position and yield an acid radical having a single carboxyl group but being of distinctly higher molecular weight. Any of such acid radicals may react with any free hydroxyl. Indeed, almost invariably and inevitably in a cogeneric mixture the simplest monocarboxy type depicted thus: ROCH CH COOH, is apt to be a minor constituent and may be actually responsible for only a comparatively small amount of the end product.

The object of aforementioned US. Patent No. 2,455,731 is to yield a thermosetting resin. As far as we are aware if one were to treat a mole of phenolformaldehyde resin with two moles of ethylene oxide so as to convert the two terminal phenolic hydroxyl radicals into ethanol radicals, such polyol could be converted into a thermosetting resin .of the kind specified in US. Patent No. 2,455,731. However, we use resins which have been oxylkylated to the extent that the resultant product is permanently fusible and not thermosetting in the usual sense. Stated another way, the resultant or reaction wih the seleced beta-lactone yields products which are organic solvent-soluble. In other words, they are soluble in solvents such as hydrocarbons, particularly aromatic hydrocarbons, including xylene, etc. They are generally soluble in alcohols, ethers, glycols, etherglycols, and the like. These derivatives can be dissolved in a mixed solvent consisting of a mixture of an oxygenated solvent and a nonoxygenated solvent. They can be prepared at the temperature of reaction herein described without yielding insoluble resins. Reference to the products being obtained at temperatures below the point of, pyrolysis, of course, does not exclude dehydration as one of the usual reactions in light of what has been said previously. i

Oxyalkylated resins can be treated with polyepoxides particularly diglycidyl ethers as described in our copending applications, Serial Nos. 349,972, filed April 20, 1953, and 343,804, filed March 20, 1953. Suchoxyalkyl'ated derivatives can be reacted withlactones as herein described in the same manner as compounds free from polyepoxide groups. This also applies to phenol-aldehyde resins which are first reacted with the polyepoxide and particularly a diglycidyl ether and then subjected to oxyalkylation. Such derivative likewise can be treated with a lactone of the kind herein described. However, these groups are not included in the instant invention.

It is to be noted that the oxyalkylated derivatives which are subjected to reaction with a suitable lactone may roughly represent two parts of the initial resin and ninetyeight percent of the alkylene oxide.

Reference is again made to US. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Attention is directed to that part of the text which appears in columns 28 and 29, lines 12 through 75, and lines 1 through 21, respectively. Reference is made to this test with the same force and effect as if it were herein included. This, in essence, means that the preferred product for resolution of petroleum emulsions of the waterin-oil type is characterized by the fact that a 50-50 solution in xylene or its equivalent, when mixed with one to three volumes of water and shaken will produce an emulsion.

For purpose of convenience, what is said hereinafter will be divided into four parts:

Part 1 is concerned with suitable phenol-aldehyde resins to be employed for reaction with monoepoxides;

Part 2 is concerned with the oxyalkylation of the previously described phenol-aldehyde resins;

Part 3 is concerned with the reactions between the oxyalkylated resins previouslydescribed and a suitable lactone such as beta-propiolactone;

Part 4 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously-described chemical compounds or reaction products.

PART' 1 This part is concernedwith the preparation. of phenol.- aldehyde resins of the kind describedin detail in US. Patent No. 2,499,370, dated March 7, 1950, to De Groote and Keiser, with the following qualifications: said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon atoms,.

as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to US. Patent No; 2,499,370, reference is made also to the following US. Patents: Nos. 2,499,- 365; 2,499,366; and 2,499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, describe phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atom also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediates for preparing the products of the present application, and reference is made to that patent for such detailed description and to Examples 1a through 103a of that patent for examples of suitable resins.

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octade'cylphenol, reference in each instance being to the difunctional phenol, such as the orthoor para-substituted;

phenol or a mixture ofthe same; Such: resins are de; scribed also in issued patents, for instance,..U.S;' Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

Itis sometimes desirable to present the resins hereinemployed in an over-simplified form which has appeared from time to time in the literature, and particularly in the patent literature, for instance, it has been stated that the composition is approximated in an idealized form by the formula in the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10' or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature.- A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6; i.e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent .bridge radical is shown as being derived from formalde-- hyde, it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

In the above formula the aldehyde employed in the resin manufacture is formaldehyde. Actually, some other aldehyde such as acetaldehyde, propionaldehyde, or butyraldehyde may be used. The resin unit can be exemplified thus:

in which R is the divalent radical obtained from the particular aldehyde employed to form the resin.

As previously stated, the preparation'of resins, the kind herein employed as reactants, is well known. See US. Patent'No. 2,499,368, dated March 7, 1950, to De Groote" :and Keiser. Resins can be made using an acid catalyst: -or' basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by' using a strong acidas a catalyst, such strong acid shouldbe neutralized. Similarly, if a strong base is used as-a catalyst it is preferable that the base be neutralized al--' "though we have found that sometimes the reaction de- :SCl'lbCd proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as .a 200th of a percent and as much as a few th of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most de-- .sirable procedure in practically every case is to have-the resin neutral.

In preparing resins one does not get a single polymer, i.e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for in :stance, one approximating 4 phenolic nuclei will have :some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractionalvalue for n as, for example, 3.5; 4.5; or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowestin price and most readily available commercially Forpurs poseof convenience suitable resins are characterized in the following table:

TABLE I Moi. wt. .Ex- R of resin ample R Position derived 1: molecule number of R trom- (based on n+2) 1 Pheny 3. 5

Tertiary butyl 3. 5 Secondary butyl- 3. 5 Oyeiohexyl 3. 5 Tertiary amyl 3. 5 Mixed secondary 3. 5

and tertiary amyi. Propy 3. 5 Tertiary hexyl 3. 5 Oetyl 3. 5 3. 6 3. 5 yl 3.5 1311 Tertiary butyl 3. 5

14a Tertiary aruyl 3. 5 1 N ony 3. 6

Tertiary butyl. 3.

Tertiary arnyi 3.

Nony do. do 3.

Tertiary butyl do Formal- 4.

dehyde.

Tertiary amyl do d 4.

Non do d 4.

Tertiary butyl ..do do 4.

Tertiary amyl n 4.

Nonyl dn do 4,

Tertiary amyl .do do 1. Oyclohexyl -do do 1.

30 Hexyl do do 1. 31a d do.. Ae etglde- 1.

?! 000 000 cum cucncncioooeootoio NO'KUI tamer Cn PART 2 There have been issued a susbtantial number of patents which give detailed description of the preparation of oxyalkylated derivatives of resins of the kind previously described. For example, see US. Patents 2,499,365; 2,499,366; 2,499,367; 2,499,368; and 2,499,370, all dated March 7, 1950, to De Groote and Keiser.

More specifially, a number of other patents have appeared in which the oxyethylation step is given with considerable detail. See, for example US. Patents 2,581,376; 2,581,377; 2,581,378; 2,581,379; 2,581,380; and 2,581,381, all dated January 8, 1952, to De Groote and Keiser. As to further examples, see US. Patent 2,602,052 dated July 1, 1952, to De Groote.

The oxypropylation or, for that matter, the treatment of resins with butylene oxide, glyc-ide, or methyl glycide, hasbeen described in the first of the series in the above mentioned patents, i.e., those issued in 1950.

Reference is made to US. Patent 2,557,081, dated June 19, 1951, to De Groote and Keiser. This particular patent describes in considerable detail resins which are first treated with propylene oxide and then with ethylene oxide or with ethylene oxide and then propylene oxide 01' With? both oxides simultaneously.

In order to avoid an extensive repetition of what is already described in detail in the patent literature, we are referring to the tables beginning in column 21 of US.- Patent 2,581,376 and extending through column 36. We have simply numbered these products beginning with 112,

aliotting, of course, five numbers to each table beginning 75 with the first table. For convenience these sixteen tables are summarized in the following table:

Para-phenyl Para-phenyl Para-secondary NorE.-For ease of comparison, blanks appear in the above table where blanks appear in previously mentioned tables in 0.8. Patent 2,581,376.

Oxypropylated derivatives comparable to 1b through b as described above can readily be obtained by sub-. stituting a molar equivalent amount of propylene oxide, i.e., 56 lbs. of propylene oxide, for example, for each 44 lbs. of ethylene oxide. We have prepared such a similar series but for sake of brevity only a few will be, included for purposes of illustrat on.

ensues TABLE nr Ph 1 Ald'h R in i p PI'OPY- one 9 y e ven es py em 0. lated lbs. lbs.- oxlde,

analog lbs Para-tertiary Formalde- 15. 72L 5.10 amyl.

.1200v 14.40 s. 24 21.00 4. s7 1 16.60 3.75 16.80 16.20 I 4.40 12. 24 16.45 8.30 22.60 5.45 22.00 3.43 18.55

; As an illustration. of oxypropylated resins involving the use of both ethylene and propylene oxide, a; reference is made to the aforementioned US. Patent 2,557,081,, dated June 19, 1951, to De Groote and Keiser. The last table in column 28 of said patent describes in detail; the. preparation of a series of oxyalkylated resins in which both propylene and ethylene oxide are employed. Simply by illustration, a series of 27 compounds are included, the description of which appears in detail in said aforementioned US. Patent 2,577,081, to De Groote and. Keiser. Note the hereto attached drawing is identical with. the drawing which appears. in said US. Patent No. 2,557,081. 1

Note the first series of nine componds, 1a through. 9d were prepared with propylene oxide, first and then ethyl-1 ene oxide. The second nine compounds, 10d through 18d inclusive, were prepared using ethylene oxide first and then propylene oxide, and the last nine compounds, 19d through 27d, were prepared by random oxyalkylation, i.e., using a mixture of the two oxides.

In the preparation of the resins, our preference is to use hydrocarbon substituted phenols, particularly parasubstituted, in which the substituted radical R contains 4 to 18 carbon atoms and particularly 4 to 14 carbonatoms. The amount of alkyleneoxide introduced may 45' 10 be comparatively large in comparison to the initial resin. For instance, there may be as much as parts by weight of an oxide or mixed oxides used for each' part by weight of resin employed. -It will be noted that the various resins. referred "to in the aforementioned" US. Patent. 2,499,370 are substantially the same type of materials as referred to in Table I. Forinstancepresin 3a of the table is substantially the same as 2a of the patent; resin 20a of the table is substantially the same as 34a of the patent; and resin 38a of the table is the same as 3a of the patent.

In reaction with polyepoxides, and particularly diepoxides, a large number of the previously described oxyalkylated resins have been employed. For convenience, the following list is selected indicating the previously described compounds and their'molecular weights. Such resins .are generally employed as a 50% solution and the polyepoxid'e employed is a 50% solution, usually both reactants being dissolved in xylene and sufilcient sodium methylate added to act as a catalyst, for instance, 1 to 2%.

TABLE v 1 Example number i TABLE IV See U.7Sd8{at.

I Ethylene Propylene Flake Ex. Resinused Resin, oxide, oxide, Wt. of caustic N 0. Ex. No. Point on lbs. lbs; lbs. xylene soda,

in above graph on ounces patent above I patent I I A 1 Tert. amyl' phenol form- 6. 1 3 1 10 1 aldehyde. B 5 d 5 4 1 10 1 O 8 3 6 I '10 1 D 2 1 21.5 2.5 25 2 E 9 1 15 9 25 2 F 6 1 10 15 25 2 G 3 1 2.5 21.5 25 2 H 7 5 1 4 10 1 I 4 do r 6 1 3 10 1 A 1 lhoultiyl phenol formr 6 3 1 10' r 1 e.

C 3' 1 6 1 10' 1', D ,1 21.5 2.5 25 2 E I 15 9 T 25 2 F 1 10 .14. 25 2 G 1 2.5 21.5 v 25: 2 H 5 I 1 4 10 1 I do 6 l 1 '3 10 1 A Nonyl phenol-formalde- 6 3 1 10 1 hyde. B 5 do 5. 4 1 10 1 O 8 3 6 1 10 1 D 2 1 21.5 2.5 25 2 A F 6 1. 10 1'4 25 2 v 11 PART 3- i As stated previously, the final reaction involves. the use of abeta lactone of the kind characterizedby beta-propiolactone and an oxyalkylated phenol-aldehyde resin of the kind previously noted. The amount of lactone used may be as little as two moles of the propiolactone per mole of oxyalkylated resin or may be as much as 3 to 6 or even 10 moles of the lactone for each hydroxyl group present in the oxyalkylated molecule. M

As is well known, beta-propiolactone reacts readily, in fact, comparable to the more reactive acid anhydrides. Generally speaking, we have conducted the reaction in the presence of an inert solvent such as benzene, toluene, xylene, or a mixture and at a temperature from the boiling point of water to slightly above that temperature. Generally speaking, the range of 100 C. to 130 C. is perfectly satisfactory and in any event we have limited the temperature to 175 or less. L

A catalyst is employed, preferably an acid catalyst present in the amount of about 2% to not over 1%. The catalyst can be any suitable inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, or may be an organic acid, such as an aromatic sulfonic acid, including paratoluene sulfonic acid. It is sometimes convenient to use a mixture of xylene, and benzene so the mixture doubles at 120 to 135 C. and permits the reaction mass to reflux at this temperature in presence of. .5% catalyst for approximately 2 to 4 hours. At the end of the reaction period the acid catalyst could be neutralized if desired and the product can be filtered.

The products can be bleached by the use of filtering" clays, char-s or the like so as to obtain products having" either a straw color or are almost water-white. Some 12 there is a tendency for the free acid value to drop off. As pointed out previously the product of reaction has a saponification value and also an acid value. The saponification valuemay be due in part to a polymerized hy- 5 droxy acid radical and also may be due in part to'an ester radical involving either an unpolymerized acid radical or a polymerized acid radical, and a hydroxyl group. There is no objection to using a higher temperature or longer period of time provided only the final products still remain soluble in xylene or an equivalent organic solvent.

Using the reactants herein described in the proportions described and under the conditions described the products of reaction are invariably organic solvent-soluble. Even if freed of solvent and heated at a somewhat higher tem-; perature the products are apt to remain fusible or thermo plastic up to their decomposition point, or gelation point;

Example 1e In a suitable reaction vessel 122.8 grams of oxyalkylat-.

ed resin, previously identified as Example 40, were mixed with 126 grams of xylene and one gram of sulfuric acid. The mixture was heated slowly to approximately C; and then 2.9 grams of beta-propiolactone added slowly.- The temperature was then raised to approximately 125 C. and-held at this point for 2 hours. At the end of this time tests showed the reaction was complete. There was no unreacted beta-propiolactone.

Table VI following gives a large number of examples in tabular form including all pertinent data.

The finished product has substantially the same appearance as the initial oxyalkylated resin except that it was somewhat more reddish in color and a bit more viscous in absence of solvent. In other instances there was a definite increase in viscosity, especially when higher ratios of the products have a yellowish amber or reddish shadeof lactone were employed.

TABLE VI Oxy- Cats.- Sol- Max Time alkyl- Amt. Amt. Molar lyst vent reac- 0! Ex. No. ated gms. Laetone gms. ratio (cone. (xylene) tlon reacresln H gms. tem tlon gms. (hrs.)

122.8 Beta-proplolectone-.. 2.9 1:2 1 126 125 2 122.8 0 14.4 1:10 1 137 115 3 28.8 1:20 1 152 3 2.9 1:2 1 145 121 2 14.4 1:10 1 156 110 3 28.8 1:20 1 170 8 1.5 1:2 2 251 118 2 7.2 1:10 2 256 115 2 14.4 1:20 2 264. 110 3 1.5 1:2 2 241 120 2 7.2 1:10 2 247 116 2 14.4 1:20 2 260 118 3 10.0 1:5 1 133 3 20.0 1:10 1 143 122 4 10.0 1:5 1 152 122 3 20.0 1:10 1 162 125 4 5.0 1:5 2 254 2 10.0 1:10 2 269 128 3 5.0 1:5 2 245 123 2 10.0 1:10 2 260 125 3 but this 1s of no significance for the uses for which the PART 4 product, in a suitable amount of xylene and benzene and then reflux in presence of the acid catalyst until no water 65 and effect to the mstant process, noting only that where shows in the phase-separating trap. We then prefer to cool the product back to 60 C. with continued stirring As to the use of conventional demulsifying agents reference is made to U.S. Patent No. 2,626,929, dated 1 January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference j should be to Example 4e, herein described. Having thus described our invention what we claim 70 as new and desire to secure by Letters Patent is:

of 2 to 4 hours.

A somewhat higher temperature can:

. 1. The process of breaking petroleum emulsions of; 1 the water-in-oil type characterized by subjecting the{ emulsion to the' action of a demulsifier includingsyrk j thetic hydrophile products obtained by the chemical be employed, and as the temperature increases itappears jfi mOdifiC fi of hydrophile Syn B 'Q i said hydrophile synthetic products being oxyalkylation products of (A) an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde-resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R O),,, in which R is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals and n is a numeral varying from 1 to 40; with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus; by reaction with (BB) a beta-lactone of the formula 12' R R H c oc=o wherein R is a radical selected from the group consisting of hydrogen and unreactive alkyl, aryl, aralkyl and cycloalkyl radicals; said reaction being conducted in a substantially anhydrous state in absence of an alkaline catalyst and at a temperature at least suificiently high to induce lactone ring cleavage, and below the point of pyrolysis; with the proviso that the products of reaction be organic solvent-soluble, the molar ratio of reactants being at least 2 moles of the lactone for each mole of oxyalkylated resin and not in excess of 6 moles of the lactone for each hydroxyl group present in the oxyalkylated phenol-aldehyde resin.

2. The process of claim 1 in which the beta-lactone employed in the chemical modification contains less than 6 carbon atoms.

3. The process of claim 1 in which the beta-lactone employed in the chemical modification is propiolactone.

4. The process of claim 1 wherein the beta-lactone employed in the chemical modification is propiolactone and the reaction is conducted in presence of an acid catalyst.

5. The process of claim 1 wherein the beta-lactone employed in the chemical modification is propiolactone and the reaction is conducted in presence of an acid catalyst at a temperature not in excess of 175 C.

6. The process of claim 1 wherein the beta-lactone employed in the chemical modification is propiolactone and the reaction is conducted in presence of an acid catalyst at a temperature not in excess of 175 C., and with the proviso that the hydrophile properties of the final reaction product in an equal weight of xylene are 14 sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

7. The process of breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including synthetic hydrophile products obtained by the chemical modification of (AA) hydrophile synthetic products; said hydrophile synthetic products being oxyalkylation products of (A) both ethylene oxide and propylene oxide; and (B) an oxyalkylation-susceptible, fusible, organic solventsoluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent C H O and C H O radicals, with the proviso that the composition of said hydrophile synthetic products, based on a statistical average and assuming completeness of reaction, and calculated back to the three oxyalkylation-step reactions, i.e., resin, ethylene oxide and propylene oxide, on a percentage weight basis must fall approximately within the area defined by the trapezoid, 1,2,3 and 4 of the chart in the accompanying drawing; by reaction with (BB) betapropiolactone; said reaction being conducted in a substantially anhydrous state in presence of an acid catalyst and at a temperature sufliciently high to induce lactone ring cleavage and below C., with the proviso that the products of reaction be organic solvent-soluble, the molar ratio of reactants being at least 2 moles of the lactone for each mole of oxyalkylated resin and not in excess of 6 moles of the lactone for each hydroxyl group present in the oxyalkylated phenol-aldehyde resin; and with the final proviso that the hydrophile properties of the final reaction product in an equal weight of xylene are suificient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

8. The process of claim 7 with the proviso that the three oxyalkylation step reactants, i.e., resin, ethylene oxide and propylene oxide on a percentage basis must fall within the area defined by the parallelogram 5, 6, 3 and 7 on the chart in accompanying drawing.

References Cited in the file of this patent UNITED STATES PATENTS 2,414,729 Fleming Ian. 21, 1947 2,430,002 De Groote et a1 Nov. 4, 1947 2,454,544 Bock et al. Nov. 23, 1948 2,507,910 Keiser et al. May 16, 1950 2,518,668 De Groote et al. Aug. 15, 1950 2,615,853 Kirkpatrick et al. Oct. 28, 1952 

1. THE PROCESS OF BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING SYNTHETIC HYDROPHILE PRODUCTS OBTAINED BY THE CHEMICAL MODIFICATION OF (AA) LHYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-ETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE; AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE-RESSIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFLUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 